Long chain hindered amines and compositions stabilized therewith

ABSTRACT

Hindered amine compounds which are substituted by a long hydrocarbon chain are useful in a number of applications where the solubility or compatibility afforded by said substitution is needed. This is seen particularly for example with white, dyed, dipped, unscented and/or scented candle wax which is effectively stabilized against discoloration and fading by the incorporation therein of a long chain hindered amine alone or in combination with a UV absorber and/or an antioxidant.

This is a divisional of application Ser. No. 09/836,100, filed Apr. 17,2001 now U.S. Pat. No. 6,465,645 B1.

This invention pertains to hindered amine compounds which aresubstituted by a long hydrocarbon chain and which are useful in a numberof applications where the solubility or compatibility afforded by saidsubstitution is needed. This is seen particularly for example withwhite, dyed, dipped, unscented and/or scented candle wax which iseffectively stabilized against discoloration and fading by theincorporation therein of a long chain hindered amine alone or incombination with a UV absorber and/or an antioxidant.

BACKGROUND OF THE INVENTION

Candles have been known for many centuries going back to the eighthcentury B.C. The nature of candles is described in Ullmann'sEncyclopedia of Industrial Chemistry, Volume A5 at pages 29-30 where itis seen that candles are made from paraffin, beeswax and stearin asbasic materials, and where a host of additives may also be present.

It is not surprising that with candles and wax becoming increasinglymore important attention was paid as to how to stabilize the saidmaterials. At the National Candle Association Meeting in Houston, 1994,R. van der Vennet presented a paper on “Antioxidants in Wax-Replacementof BHT” touting the use of Vitamin E (tocopherol) as an antioxidant toprevent the yellowing of wax when oxidized. WO 94/13736 describes thesame invention.

EP 359,488 A3 and EP 133,964 B1 describe stabilized waxes used incosmetics where the waxes are the same or similar to those used incandles.

EP 5,922 A1 describes lip cosmetics where the waxes are useful inlipsticks and are related to those useful in candles.

U.S. Pat. No. 5,879,694 describes in detail transparent gel candles bothin composition and structure. The use of BHT as an antioxidant ismentioned.

At the National Candle Association Technical Meeting on Apr. 16, 1998,F. A. Ballentine et al., presented a paper entitled “Inhibiting ColorFading of Dyed Candles with CYASORB® Light Absorbers” in which thegeneral theories of thermal oxidation and photodegradation are discussedalong with data on the effect of light absorbers on color stability ofdyed candle waxes. The light absorbers compared are4-octyloxy-2-hydroxybenzophenone UV-531; 4-methoxy-2-hydroxybenzophenoneUV-9; 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole UV-5365;2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole UV-5411 and2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole UV-2337).

U.S. Pat. No. 5,964,905 teaches dyed and scented candle gels containingtriblock copolymers and a hydrocarbon oil of high flash point. Thisreference teaches that a light (UV) absorber may be used to improve theshelf stability of the candle color when exposed to visible orultraviolet light. Two preferred absorbers are ethylhexylp-methoxycinnamate (PARSOL® MCX, Roche) and2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (CYASORB® 5411,Cytec).

WO 00/22037 teaches the stabilization of solid, shaped and colored waxarticles, including candles, using a malonate UV absorber which mayoptionally contain a hindered amine moiety as part of the malonatecompound structure. The wax articles are dyed with a variety of oilsoluble dyes and pigments. The samples protected by dimethyl p-methoxy-benzylidinemalonate exhibited better resistance to discoloration thatdid samples stabilized with selected benzotriazole or benzophenone UVabsorbers.

Japanese Hei 3-278554 teaches that wax crayons (drawing materials)colored by organic pigments can be stabilized by a hindered amine and/orbenzotriazole.

In respect to wax stabilization, the use of selected hindered aminesand/or benzotriazole UV absorbers is also known in the prior art as seenin U.S. Pat. Nos. 3,530,084; 4,379,721; 4,616,051 and 5,964,905 andcopending application Ser. Nos. 09/495,495, 09/495,496 and 09/741,583.

U.S. Pat. Nos. 4,046,737; 4,021,432 and 4,049,647 teach piperidinederivatives having substituted by alkyl, alkenyl or alkynyl groups of 1to 20 carbon atoms.

Japanese Sho 57-137,358 describes piperidine derivatives substituted onthe N-atom by a group containing a polymerizable double bond.

EP 300,160 and Japanese Hei 11-263,884 depict piperidine dervativessubstituted on the 4-position by a monocarboxylic acid of 16 to 24carbon atoms. The resulting hindered amine is useful for stabilizinglubricating oils, cosmetics and polyolefins.

U.S. Pat. No. 4,376,836 disclose triazylaminotriazines substituted byhindered piperidine groups where the longest chain in said moleculescontain 18 carbon atoms. These molecules are used to stabilizepolyolefins.

U.S. Pat. No. 4,319,030 teaches alkylated diaza-spirodecanes which maycontain alkyl groups of 1 to 30 carbon atoms. These compounds are usedas stabilizers for polyolefins.

U.S. Pat. No. 4,986,932 describes polyolefin compositions containing abenzotriazole or benzophenone UV absorber and a hindered piperidinesubstituted on the 4-position by a ester group containing 16-24 carbonatoms.

U.S. Pat. No. 4,308,362 discloses copolymers of polymerizable hinderedpiperidine derivatives which are useful for the stabilization ofpolyolefins.

U.S. Pat. No. 4,198,334 teaches substituted malonic acid derivativescontaining hindered piperidine derivatives which may be substituted withalkyl groups of 1 to 20 carbon atoms.

U.S. Pat. No. 4,496,649 describes color photographic recording materialcontaining hindered piperidine derivatives, but containing aromaticmoieties in the molecules.

U.S. Pat. No. 4,141,883 discloses 2,2,6,6-tetraalkylpiperidine compoundssubstituted on the 4-position by an alkyloxy or acyloxy group of 1 to 18carbon atoms. These materials are useful for stabilizing polyolefins.

U.S. Pat. No. 4,471,417 teaches poly-bis-triazinylimides which containhindered amine piperidine moieties and alkyl groups of 1 to 18 carbonatoms. These compounds are useful for stabilzing polyolefins.

U.S. Pat. No. 4,533,688 discloses tris(piperidylaminotriazylamino)compounds which contain alkyl moieties of 1 to 18 carbon atoms. Thesecompounds are useful for the stabilization of polyolefins

U.S. Pat. No. 5,204,473 and copending application Ser. No. 09/257,711describe hindered amine compounds related to the instant compounds, butwithout the long chain substitution.

None of these references teach the instant long chain hindered aminecompounds themselves or the superior performance provided when said longchain hindered amine compounds are used alone or in conjunction with aUV absorber and/or antioxidant to stabilize candle wax and othercompositions subject to degradation.

OBJECTS OF THE INVENTION

The object of the invention is to provide for hindered amine compoundssubstituted by a long chain hydrocarbon moiety.

Another object of the invention is to provide for a white and unscented;white and scented; dyed and unscented; dyed and scented; dipped andunscented; or dipped and scented candle wax stabilized by a long chainhindered amine or UV absorber compound alone or in combination with a UVabsorber and/or antioxidant.

Still another object of the invention is thermoplastic resincompositions stabilized with the instant hindered amines, particularlypolyolefins and polyesters.

Detailed Disclosure

The instant invention pertains to a compound of formula 1 to 6

G₁, G₂, G₃, and G₄ are independently alkyl of 1 to 8 carbon atoms, or G₁and G₂ together are pentamethylene, or G₃ and G₄ together arepentamethylene;

E₅ is OE₉ or —O—E—(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 15 carbon atoms,aryl of 6 to 10 carbon atoms or said aryl substituted by one to threealkyl of 1 to 4 carbon atoms; or a group of formula IV

E₁₁ to E₁₅ are independently hydrogen, halogen, nitro, cyano, alkyl of 1to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms,alkoxy or 1 to 18 carbon atoms, phenylalkoxy of 7 to 15 carbon atoms,aryloxy of 6 to 10 carbon atoms, alkylcarbonyloxy of 2 to 18 carbonatoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15carbon atoms, sulfo or phosphono, or any two vicinal substituentsconnected together to form a mono- or polycyclic ring;

E is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in E, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atom of E;

R₂ is T₁, —CO—T₁, —CO—X—T₁, —(CH₂)_(m)—CO—X—T₁, —(CH₂)_(p)—X—CO—T₁,—CO—(CH₂)_(m)—CO—X—T₁, or —CO—(CH₂)_(p)—X—CO—T₁;

m is 1 to 12;

p is 1 to 12;

T₁ is straight or branched chain alkyl of 19 to 100 carbon atoms, orsaid alkyl substituted by one hydroxyl group and interrupted by one oxamoiety, or a mixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, propylene, trimethylene,1,2-butylene or tetramethylene, and n is 4 to 49 so that the totalnumber of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms;

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms;

R₆ is T₁, —X—T₁, —(CH₂)_(m)—CO—X—T₁, —(CH₂)_(p)—X—CO—T₁,X—(CH₂)_(m)—CO—X,-T₁, or X—(CH₂)_(p)—X₁—CO—T₁;

R₇ and R₈ are independently chlorine, alkoxy of 1 to 18 carbon atoms,—O—T₂, amino substituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18 carbonatoms, —N(alkyl)T₂ with alkyl of 1 to 18 carbon atoms, —N(alkyl)₂ of 2to 36 carbon atoms, —X—T₁, X—(CH₂)_(m)—CO—X₁-T₁, orX—(CH₂)_(p)—X₁—CO—T₁;

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, oxyl, hydroxyl, straight or branched chain alkyl of 1 to24 carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, benzyl, acetyl, —CH₂CH(OH)-E₈, —OE₉, or, —OE(OH)_(b);

E₈ is hydrogen, methyl, ethyl or phenyl;

R₁₀ is hydrogen or an alkyl group of 1 to 18 carbon atoms;

q is 2 to 8;

y is 1 to 10;

R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 18carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms suchas tert-octylamino, —N(alkyl)T₂ with alkyl of 1 to 8 carbon atoms,—N(alkyl)₂ of 2 to 16 carbon atoms, —X—T₁, X—(CH₂)_(m)—CO—X₁-T₁, orX—(CH₂)_(p)—X₁—CO—T₁;

R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorineand once by R₁₅, or s-triazinyl substituted twice by R₁₅ with thecondition that the two R₁₅ substituents may be different;

R₁₇ is chlorine, amino substituted by alkyl of 1 to 18 carbon atoms orby T₂, —N(alkyl)T₂ with alkyl of 1 to 8 carbon atoms, —N(alkyl)₂ of 2 to16 carbon atoms, or the group T₃

R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by—N(alkyl)₂ of 2 to 16 carbon atoms or s-triazinyl substituted twice by—N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms;

with the proviso that at least one of R₂, R₆, R₇, R₈, or R₁₅ is a groupwhich contains a T₁ moiety.

It is understood that whether T₁ is an alkyl group or a —(R—O)_(n)—R—OG₅group that such moieties are usually a mixture of molecular weightsfalling within the scope of the total number of atoms indicated.

When R is ethylene, the group T₁ is —(CH₂CH₂O)_(n)—CH₂CH₂OG₅ where n is9 to 49.

When R is propylene, the group T₁ is —(CH(CH₃)CH₂O)_(n)—CH(CH₃)CH₂OG₅where n is 6 to 32.

When R is trimethylene, the group T₁ is —(CH₂CH₂CH₂O)_(n)—CH₂CH₂CH₂OG₅where n is 6 to 32.

When R is tetramethylene, the group T₁ is—(CH₂CH₂CH₂CH₂O)_(n)—CH₂CH₂CH₂CH₂OG₅ where n is 4 to 24. Also R is also1,2-butylene so that T₁ is —(CH(CH₂CH₃)CH₂O)_(n)—CH(CH₂CH₃)CH₂OG₅ wheren is 4 to 24.

Other embodiments of formula (1) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, or alkoxy or 1 to18 carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol; most preferably E—OH is formed from1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol or

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

R₂ is —CO—T₁, —CO—X—T₁, —(CH₂)_(m)—CO—X—T₁, or —(CH₂)_(p)—X—CO—T₁;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms, or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, or propylene, and n is 6 to49 so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—; and

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms.

Other embodiments of formula (2) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, or alkoxy or 1 to18 carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol;

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

R₂ is —CO—T₁, —CO—X—T₁, —(CH₂)_(m)—CO—X—T₁, or —(CH₂)_(p)—X—CO—T₁;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms, or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, or propylene, and n is 6 to49 so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—; and

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms.

Other embodiments of formula (3) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, or cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, or alkoxy or 1 to18 carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol;

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms, or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, or propylene, and n is 6 to49 so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, or straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms; and

R₆ is —X—T₁, X—(CH₂)_(m)—CO—X₁-T₁, or X—(CH₂)_(p)—X₁—CO—T₁.

Other embodiments of formula (4) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, or cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy or 1 to 18carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol;

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1,-tris(hydroxymethyl)methane,2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms, or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, or propylene and n is 4 to49 so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms;

R₇ and R₈ are independently alkoxy of 1 to 18 carbon atoms, —O—T₂, aminosubstituted by 2-hydroxyethyl, —N(alkyl)T₂ with alkyl of 1 to 18 carbonatoms, —X—T₁, X—(CH₂)_(m)—CO—X₁-T₁, or X—(CH₂)_(p)—X₁—CO—T₁;

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, hydroxyl, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, benzyl, acetyl, —OE₉, or —OE(OH)_(b).

Other embodiments of structure (5) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, or cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, or alkoxy or 1 to18 carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol;

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene or propylene and n is 4 to 49so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms;

R₇ and R₈ are independently alkoxy of 1 to 18 carbon atoms, —O—T₂, aminosubstituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18 carbon atoms,—N(alkyl)T₂ with alkyl of 1 to 18 carbon atoms, —X—T₁,X—(CH₂)_(m)—CO—X₁-T₁, or X—(CH₂)_(p)—X₁—CO—T₁;

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, oxyl, hydroxyl, straight or branched chain alkyl of 1 to24 carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, acetyl, —OE₉, or, —OE(OH)_(b);

R₁₀ is hydrogen or an alkyl group of 1 to 18 carbon atoms, and

q is 4 to 8.

Other embodiments of structure (6) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenylof 3 to 24 carbon atoms, or cycloalkenyl of 5 to 12 carbon atoms; or agroup of formula IV

E₁₁ to E₁₅ are independently hydrogen, F, Cl, Br, nitro, cyano,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, or alkoxy or 1 to18 carbon atoms;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol;

when b is 2, E—OH is respectively a carbon-centered radical or diradicalformed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol;

when b is 3, E—OH is respectively a carbon-centered radical formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol;

m is 1 to 4;

p is 1 to 4;

T₁ is straight or branched chain alkyl of 19 to 80 carbon atoms or amixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene or propylene and n is 4 to 49so that the total number of carbon atoms in T₁ is at least 20;

G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms;

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms;

R₇ and R₈ are independently alkoxy of 1 to 18 carbon atoms, —O—T₂, aminosubstituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18 carbon atoms,—N(alkyl)T₂ with alkyl of 1 to 18 carbon atoms, —X—T₁,X—(CH₂)_(m)—CO—X₁-T₁, or X—(CH₂)_(p)—X₁—CO—T₁;

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, oxyl, hydroxyl, straight or branched chain alkyl of 1 to24 carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, acetyl, —OE₉, or, —OE(OH)_(b);

R₁₀ is hydrogen or an alkyl group of 1 to 18 carbon atoms,

q is 4 to 8;

y is 1 to 10;

R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms suchas tert-octylamino, —X—T₁, X—(CH₂)_(m)—CO—X₁—T₁, orX—(CH₂)_(p)—X₁—CO—T₁;

R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorineand once by R₁₅;

R₁₇ is amino substituted by alkyl of 1 to 18 carbon atoms or by T₂,—N(alkyl)T₂ with alkyl of 1 to 8 carbon atoms, —N(alkyl)₂ of 2 to 16carbon atoms, or the group T₃

R₁₈ is hydrogen.

Still other embodiments of formula (1) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 12 carbon atoms, orcycloalkyl of 5 to 10 carbon atoms;

b is 1;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol;

R₂ is —CO—T₁;

T₁ is straight or branched chain alkyl of 19 to 60 carbon atoms, or amixture of such alkyl moieties.

Still other embodiments of formula (2) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 12 carbon atoms, orcycloalkyl of 5 to 10 carbon atoms;

b is 1;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol;

R₂ is —CO—T₁;

T₁ is straight or branched chain alkyl of 19 to 60 carbon atoms, or amixture of such alkyl moieties; or

R₄ is hydrogen or methyl.

Still other embodiments of formula (3) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 12 carbon atoms, orcycloalkyl of 5 to 10 carbon atoms,

b is 1;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol or 2-propanol;

T₁ is straight or branched chain alkyl of 19 to 60 carbon atoms, or amixture of such alkyl moieties;

X is —O—; and

R₆ is —X—T₁.

Still other embodiments of formula (4) are

G₁, G₂, G₃, and G₄ are each methyl;

E₅ is OE₉ or —O—E-(OH)_(b);

E₉ is straight or branched chain alkyl of 1 to 12 carbon atoms, orcycloalkyl of 5 to 10 carbon atoms,

b is 1;

when b is 1, E—OH is respectively a carbon-centered radical formed from2-methyl-2-propanol;

T₁ is straight or branched chain alkyl of 19 to 60 carbon atoms, or amixture of such alkyl moieties; or

X and X₁ are independently —O—, or —N—(R₄)—;

R₄ is hydrogen or methyl;

R₇ and R₈ are independently —O—T₂, —N(alkyl)T₂ with alkyl of 1 to 18carbon atoms, —X—T₁, or X—(CH₂)_(p)—X₁—CO—T₁;

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, hydroxyl, straight or branched chain alkyl of 1 to 12carbon atoms, acetyl, —OE₉, or —OE(OH)_(b).

In another embodiment of the instant invention, the long chain hinderedamine compound is

(a)2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine;

(b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine;

(c) 4-C₄₀-C₆₀alkanoyloxy-2,2,6,6-tetramethyl-1-methoxypiperidine;

(d) 4-C₂₀-C₄₀alkanoyloxy-2,2,6,6-tetramethyl-1-octyloxypiperidine;

(e)4-C₂₀-C₄₀alkanoyloxy-2,2,6,6-tetramethyl-1-(2-methyl-2-hydroxypropyloxy)piperidine;

(f)4-C₄₀-C₆₀alkanoyloxy-2,2,6,6-tetramethyl-1-(2-methyl-2-hydroxypropyloxy)piperidine;

(g)4-(N-methyl-N-C₂₀-C₄₀alkanoyl)amino-2,2,6,6-tetramethyl-1-methoxypiperidine;

(h)4-(N-methyl-N—C₂₀-C₄₀alkanoyl)amino-2,2,6,6-tetramethyl-1-(2-methyl-2-hydroxy-propyloxy)piperidine;

(i) C₂₀-C₄₀alkyl 1-methoxy-2,2,6,6-tetramethylpiperidin-4-ylcarboxylate;

(j) C₄₀-C₆₀alkyl1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ylcarboxylate;

(k) C₂₀-C₄₀alkyl1-(2-methyl-2-hydroxypropyloxy)-2,2,6,6-tetramethylpiperidin-4-ylcarboxylate;

(l)2,4-bis[N-n-butyl-N-(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine;

(m)2,4-bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yloxy)-6-(C₂₀-C₄₀alkyloxy)-s-triazine;

(o)2,4-bis{N-n-butyl-N-[1-(2-methyl-2-hydroxypropyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]amino}-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine;or

(p)2,4-bis[-(2-methyl-2-hydroxypropyloxy)-2,2,6,6-tetramethylpiperidin-4-yloxy)-6-(C₄₀-C₆₀alkyloxy)-s-triazine.

In still another embodiment of the instant invention, the long chainhindered amine compound is

(a)2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine;or

(b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine.

The instant invention pertains to a composition which comprises

(a) candle wax which is white and unscented; white and scented; dyed andunscented; dyed and scented; dipped and unscented; or dipped andscented, and

(b) an effective stabilizing amount of a combination of

(i) a long chain hindered amine piperidine compound of formula 1, 2, 3,4, 5 or 6 as described above;

(ii) a UV absorber or an antioxidant, or a UV absorber and anantioxidant

wherein the ratio by weight of (i) to (ii) is from 10:1 to 1:10.

It should be noted that, although the long chain hindered aminesdescribed in detail in this application are those derived from2,2,6,6-tetraalkylpiperidine moieties, other types of hindered aminessuch as those containing morpholinones, piperazinones, piperazindiones,oxazolidines, imidazolines and the like could also be modified toattached long chain alkyl moieties which would make them particularlysuitable for the stabilization of thermoplastic resins such aspolyolefins or polyesters and the stabilization of candle wax.

In another embodiment of the invention, the ratio by weight of (i) to(ii) is from 4:1 to 1:4.

Another embodiment of the invention is where the ratio by weight of (i)to (ii) is from 2:1 to 1:2.

In still another embodiment of the invention, the effective amount ofthe UV absorber plus the long chain hindered amine compound in thecandle wax is 0.01 to 10% by weight based on the wax.

Another embodiment of the invention is where the effective amount of theUV absorber plus long chain hindered amine compound in the candle wax is0.1 to 2% by weight based on the wax.

Another embodiment of the invention is where the effective amount of theUV absorber plus long chain hindered amine compound in the candle wax is0.1 to 0.5% by weight based on the wax.

The UV absorber of component (ii) is a benzotriazole, a benzophenone, anα-cyanoacrylate, an oxanilide, an s-triazine, a cinnamate, a malonate, abenzoate or a salicylate, or a mixture thereof.

In another embodiment of the invention, the UV absorber is abenzotriazole, a benzophenone or an s-triazine.

Examples of the UV absorbers useful in the instant invention are

(a) 4-octyloxy-2-hydroxybenzophenone;

(b) 4-methoxy-2-hydroxybenzophenone;

(c) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;

(d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole;

(e) 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

(f) octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(g) 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(h) 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;

(i) 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(j) 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

(k) 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;

(l) 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;

(m) 2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

(n) 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

(o)2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

(p)2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

(q)2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

(r) 2-ethylhexyl p-methoxycinnamate;

(s) 4-methoxy-2,2′-dihydroxybenzophenone;

(t) 4,4′dimethoxy-2,2′-dihydroxybenzophenone;

(u)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

(v) 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

(w)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;

(x)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5-α-cumylphenyl]-s-triazine;

(y) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine withoctyl α-haloacetate; or

(z) the mixture of3,3;3,5;5,5-methylene-bis[2,4-bis(2,4-dimethylphenyl)]-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxyphenyl)]-s-triazine.

Still other examples of UV absorbers useful in the instant invention are

(a) 4-octyloxy-2-hydroxybenzophenone;

(b) 4-methoxy-2-hydroxybenzophenone;

(d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole;

(o)2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

(p)2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

(q)2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;

(y) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine withoctyl α-haloacetate; or

(z) the mixture of3,3;3,5;5,5-methylene-bis[2,4-bis(2,4-dimethylphenyl)]-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxyphenyl)]-s-triazine.

Another embodiment of the instant invention involves a compositionwherein the antioxidant is a phenolic antioxidant, phosphite, nitrone,amine oxide or hydroxylamine, or mixture thereof.

Examples of the above-embodiment are wherein the effective amount of UVabsorber in combination with the long chain hindered amine compound andan antioxidant is 0.01 to 10% by weight based on the wax.

Another embodiment is where the effective amount of UV absorber incombination with the long chain hindered amine compound and anantioxidant is 0.1 to 2% by weight based on the wax.

Still another embodiment is where the effective amount of UV absorber incombination with the long chain hindered amine compound and anantioxidant is 0.1 to 0.5% by weight based on the wax.

Examples of the antioxidants useful in this invention are

n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),

di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,

thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,

3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),

2,6-di-tert-butyl-p-cresol,

2,2′-ethylidene-bis(4,6-di-tert-butylphenol),

1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate,

1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,

1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,

3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol,

hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,

N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),

calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),

ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],

octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,

bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide,

N,N-di-(C₁₂-C₂₄alkyl)-N-methyl-amine oxide, or

N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine bydirect oxidation.

Still other embodiments of antioxidants useful in the instant inventionare

neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,

2,6-di-tert-butyl-p-cresol, or

2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The instant invention pertains to a composition which comprises

(a) a thermoplastic resin, and

(b) an effective stabilizing amount of a combination of a long chainhindered amine piperidine compound of formula 1, 2, 3, 4, 5 or 6 asdescribed above.

Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

Most preferably, the polymer is a polyolefin or polycarbonate,especially polyethylene or polypropylene; most especially polypropylene.

In another preferred embodiment of the instant invention, the organicmaterial is a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

Most preferably, the resin is a thermoset acrylic melamine resin or anacrylic urethane resin.

In yet another preferred embodiment of the instant invention, theorganic material is a recording material.

The recording materials according to the invention are suitable forpressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

The recording materials according to the invention are distinguished byan unexpected improvement in quality, especially with regard to thefastness to light.

The recording materials according to the invention have the constructionknown for the particular use. They consist of a customary carrier, forexample, paper or plastic film, which has been coated with one or morelayers. Depending on the type of material, these layers contain theappropriate necessary components, in the case of photographic materials,for example, silver halide emulsions, dye couplers, dyes and the like.Material particularly suitable for ink jet printing has a layerparticularly absorptive for ink on a customary carrier. Uncoated papercan also be employed for ink jet printing. In this case the paper actsat the same time as the carrier material and as the ink-absorbent layer.Suitable material for ink jet printing is, for example, described inU.S. Pat. No. 5,073,448 which is incorporated herein by reference.

The recording material can also be transparent as, for example, in thecase of projection films.

The compounds of formula 1, 2, 3, 4, 5 or 6 can be incorporated into thecarder material as early as the production of the latter, in theproduction of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula 1, 2, 3, 4, 5 or 6 or to addthe compounds to the coating composition.

Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together; the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula 1, 2, 3, 4, 5 or 6 can be easilyincorporated into the coating composition.

The recording material according to this invention preferably contains 1to 5000 mg/m², in particular 50-1200 mg/m², of a compound of formula 1,2, 3, 4, 5 or 6.

As already mentioned, the recording materials according to the inventionembrace a wide field. The compounds of formula 1, 2, 3, 4, 5 or 6 can,for example, be employed in pressure-sensitive copying systems. They canbe introduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

Photocopying systems using light-sensitive microcapsules which aredeveloped by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

Photographic materials which can be stabilized are photographic dyes andlayers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. In color photographic materials, couplers and dyes are alsoprotected against photochemical decomposition.

The instant compounds can be used for all types of color photographicmaterials. For example, they can be employed for color paper, colorreversal paper, direct-positive color material, color negative film,color positive film, color reversal film and the like. They arepreferably used inter alia for photographic color material whichcontains a reversal substrate or form positives.

Color-photographic recording materials usually contain, on a support, ablue-sensitive and/or a green-sensitive and/or a red-sensitive silverhalide emulsion layer and, if desired, a protection layer, with theinstant compounds being, preferably, either in the green-sensitive orthe red-sensitive layer or in a layer between the green-sensitive andthe red-sensitive layer or in a layer on top of the silver halideemulsion layers.

The compounds of formula 1, 2, 3, 4, 5 or 6 can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

The instant compounds can also be employed in inks, preferably for inkjet printing, for example, as described in U.S. Pat. No. 5,098,477 whichis incorporated herein by reference.

The compounds of this invention exhibit superior hydrolytic stability,handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

The methodology to make the instant compounds is described in the priorart. The intermediates needed to make the instant compounds are largelyitems of commerce.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EM), LLDPE/EVA, LLDPE/EM and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-1-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

2,2′-thio-bis-(4-octylphenol)

4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2′-methylene-bis-(6-nonyl-4-methylphenol)

2,2′-methylene-bis-[6-α-methylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4′-methylene-bis-(2,6-di-tert-butylphenol)

4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example.

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example.

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.9. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-,3′,5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-,5-chloro-3′,5′-di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl-,3′-sec-butyl-5′-tert-butyl-, 4′-octoxy, 3′,5′-di-tert-amyl-,3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2′,4′-trihydroxy-and 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl) -resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl)sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetra-methylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

2.7. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalic acid diamide,N-salicylal-N′-salicyloyl-hydrazine, N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite,tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecyl-pentaerythritoldiphosphite, di-(2,4,6-tri-tert-butylphenyl)-pentaerythritoldiphosphite, di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritoldiphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312,or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones listedunder 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list) and peroxide-destroying compounds(item 5.) of the list.

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dio ne,tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane,tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate,mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)-nonanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine;condensation product of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy;condensation product of4-hydroxy-1-(2-hydroxy-ethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; condensationproduct of4-hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy;1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine;or 1-(2-hydroxy-2-methylpropoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,the polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)-nonanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine;condensation product of4hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy;condensation product of4-hydroxy-1-(2-hydroxy-ethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; condensationproduct of4-hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy;1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine;or 1-(2-hydroxy-2-methylpropoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine.

The instant composition can additionally contain a UV absorber selectedfrom the group consisting of the s-triazines, the oxanilides, thehydroxybenzophenones, benzoates and the α-cyanoacrylates.

Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[₂-hydroxy-3-(α,α-dimethylbenzyl)-5-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine;and

2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexybxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99-123). Othercrosslinking agents include glycouril resins, blocked isocyanates orepoxy resins.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention areapplicable for use in non-acid catalyzed thermoset resins such as epoxy,epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionallymodified with silicon, isocyanates or isocyanurates. The epoxy andepoxy-polyester resins are crosslinked with conventional crosslinkerssuch as acids, acid anhydrides, amines and the like. Correspondingly,the epoxide may be utilized as the crosslinking agent for variousacrylic or polyester resin systems that have been modified by thepresence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

When water-soluble, water miscible or water dispersible coating aredesired ammonium salts of acid groups present in the resin are formed.Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

The instant invention also pertains to a photographic materialstabilized against degradation induced by light which comprises

(a) a photographic material, and

(b) an effective stabilizing amount of a compound of formula 1, 2, 3, 4,5 or 6 as defined above.

The instant invention additionally pertains to a composition stabilizedagainst degradation induced by heat, oxygen or light which comprises

(a) a thermoset composition, and

(b) an effective stabilizing amount of a compound of formula 1, 2, 3, 4,5 or 6 as defined above.

The thermoset resins of component (a) are selected from the groupconsisting of a thermoset acrylic melamine resin, an acrylic urethaneresin, an epoxy carboxy resin, a silane modified acrylic melamine, anacrylic resin with carbamate pendant groups crosslinked with melamine oran acrylic polyol crosslinked with melamine containing carbamate groups.

The instant invention additionally pertains to a composition stabilizedagainst degradation induced by heat, oxygen or light which comprises

(a) a thermoplastic composition, and

(b) an effective stabilizing amount of a compound of formula 1, 2, 3, 4,5 or 6 as defined above.

The thermoplastic resin of component (a) includes a polyolefin,polycarbonate, a styrenic, ABS, a polyamide (nylon), a polyester, apolyurethane, a polyacrylate, a polyimide, a rubber modified styreneresin, poly(vinyl chloride), poly(vinyl butyral), polyacetal(polyoxymethylene), or blends or copolymers such aspoly(ethylene/1,4-cyclohexylenedimethylene terephthlate) PETG or anethylene/acrylic acid copolymer or salt thereof (ionomer).

Still another embodiment of the thermoplastic resin is a polyester whichis poly(ethylene terephthalate), poly(butylene terephthlate) orpoly(ethylene 2,5-naphthalenedicarboxylate) PEN or a copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthlate) PETG.

Still another embodiment of the thermoplastic resin is a polyolefinwhich is polyethylene or polypropylene; or is polypropylene.

The thermoplastic resin of component (a) is a polyamide which ispoly(m-phenylene isophthalamide), nylon 6 or nylon 66.

The thermoplastic resin of component (a) is a polyimide which ispoly(p-phenylene pyromellitimide).

The instant invention additionally pertains to a composition stabilizedagainst degradation induced by heat, oxygen or light which comprises

(a) dyed or pigmented polypropylene, polyamide or polyester fibers, and

(b) an effective stabilizing amount of a compound of formula 1, 2, 3, 4,5 or 6 as defined above.

One embodiment of the invention is where the fibers of component (a) arepigmented polypropylene fibers.

It should be noted that candles contain a host of various components.The base materials may be made up of the following:

paraffin wax,

natural oils,

polyamide plus fatty acid/ester,

fatty acids such as stearin,

opacifiers,

beeswax,

glycerides plus oxidized wax,

alcohols, and

ethylene oligomers.

Candles also contain a number of additives such as the following:

mold release agents,

fragrances,

insect repellants or insecticides,

hardeners,

crystal modifiers,

clarifiers,

guttering reducers,

colorants,

f.p. control agents,

stretchability improvers,

gelling agents,

extrusion aids, and

vortex reducers.

Each of the various components are meant to control or modify theproperties of the candle to insure proper burning, reduce channelling,aid in uniform melting, and the like. The colorants and fragrancesobviously are there to provide the proper color, scent or otheraesthetic appeal.

Of increasing importance are the transparent gel candles which look likeclear glass, but which burn like a classical candle. As is discussed indetail in U.S. Pat. No. 5,879,694, the relevant parts of which areincorporated herein by reference, these gel candles usually contain acopolymer selected from the group consisting of a triblock, radialblock, diblock or multiblock copolymer classically made up of at leasttwo thermodynamically incompatible segments containing both hard andsoft segments. Typical of such block copolymers is KRATON® (ShellChemical Co.) which consists of block segments of styrene monomer unitsand rubber monomer or comonomer units. The most common structure foundin KRATON® D series is a linear ABA block with styrene-butadiene-styrene(SBS) or styrene-isoprene-styrene (SIS).

The following examples are meant for illustrative purposes only and arenot to be construed to limit the instant invention in any mannerwhatsoever.

Raw Materials

Wax samples are supplied by the Candle-Lite Corporation. These samplescontain dyes and fragrances.

The UV absorbers and hindered amine stabilizers are obtained from theCiba Speciality Chemicals Corporation.

Sample Preparation

The wax samples obtained from the Candle-Lite Corporation alreadycontain a dye and a fragrance (scent). In these cases, the wax is meltedand the appropriate stabilizer(s) is (are) added and dissolved in themolten wax. The stabilized wax is then poured into five (5) 44 mmdiameter aluminum pans giving five (5) wax disks.

Sample Exposure

Triplicate samples of each disk are exposed under a bank of six (6)cool-white fluorescent lamps (40 watts) or under a bank of six (6) UVlamps having a wavelength of 368 nm with the test samples being twelve(12) inches (30.48 cm) below the lamps.

Dye color fade (or color change) is measured by a Macbeth ColorEyeSpectrophotometer with a 6 inch integrating sphere. The conditions are:10 degree observer; D65 illuminant and 8 degree viewing angle.

Initial color measurements are taken using the above parameters. The L,a and b values are calculated using the CIE system from the reflectancevalues. Yl is calculated from the L, a and b values. Subsequentmeasurements are taken at specified intervals. Delta L, a, b and Ylvalues are simply the difference between the initial values and thevalues at each interval. Delta(Δ) E is calculated as follows:

[(Delta L)²+(Delta a)²+(Delta b)²]^(1/2)=Delta E.

EXAMPLE 12,4-Bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine

2,4-Bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethyl)amino-s-triazine(19.0 g, 0.025 mol), performacid 350 (12.0 g, 0.025 mol,Baker-Petrolite, C₂₀-C₄₀alkanoic acid), toluene (430 g, 4.67 mols),dicyclohexylcarbodiimide (5.5 g, 0.027 mol) and dimethylaminopyridine(0.4 g, 0.003 mol) are charged to a laboratory reactor. The reactorcontents are heated to 95-100° C. and held there for six hours. Thereaction mass is filtered hot through a small pad of silica gel. Thesolvent is removed by distillation and replaced with 300 mL of acetone.The resultant solution is filtered hot and the acetone is distilled offunder reduced pressure. The title compound is obtained in a yield of17.5 g, (58%) as a white solid melting with three melting point ranges32-38° C.; 47° C. and 56° C. The structure is consistent with a mixtureof esters of varying chain lengths and is confirmed by ¹Hnmr and massspectrometry.

EXAMPLE 21-Cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine

1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine (12.8 g, 0.05mol) and performacid 350 (24 g, 0.05 mol, C₂₀-C₄₀alkanoic acid,Baker-Petrolite) are reacted together following the procedure ofExample 1. The title compound is obtained in a yield of 9 g (25%) as awhite solid with a melting point range of 35-41° C. The structure isconsistent with a mixture of esters of varying chain lengths and isverified by ¹Hnmr and mass spectrometry.

EXAMPLE 3 Color Fade of Pink Scented Candle Wax under UV Lamp Exposure

A variety of different stabilizers are evaluated in pink scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 32 days Blank (no add) 21.10 A (0.3%) 7.97 D(0.3%) 16.24 B (0.15%) + 11.15 C (0.15%) A (0.15%) + 5.72 E (0.15%) A(0.15%) + 3.76 E (0.3%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMMASORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine,the compound of instant Example 1

These data show that the instant compound (Compound E) in combinationwith a UV absorber protects the pink scented candle wax from unwanteddiscoloration far better than conventional stabilizer systems.

EXAMPLE 4 Color Fade of Gray Scented Candle Wax under Fluorescent LampExposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 29 days Blank (no add) 15.72 A (0.3%) 9.88 B(0.15%) + 8.01 C (0.15%) A (0.15%) + 3.58 E (0.15%) A (0.15%) + 3.87 F(0.15%) G (0.15%) + 6.12 E (0.15%) G (0.15%) + 6.02 F (0.15%) G(0.15%) + 6.54 F (0.3%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMMASORB ®81, CIBA. E is2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine,the compound of instant Example 1. F is1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine, thecompound of instant Example 2. G is2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine,TINUVIN ® 400, CIBA.

These data show that an instant compound (Compound E or F) incombination with a UV absorber, particularly a benzotriazole UVabsorber, protects the gray scented candle wax from unwanteddiscoloration far better than conventional stabilizer systems.

EXAMPLE 5 Color Fade of Gray Scented Candle Wax under UV Lamp Exposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 18 days Blank (no add) 29.97 A (0.3%) 8.82 B(0.15%) + 10.21 C (0.15%) A (0.15%) + 5.04 H (0.15%) A (0.15%) + 4.29 E(0.15%) A (0.15%) + 4.76 F (0.15%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMMASORB ®81, CIBA. E is2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine,the compound of instant Example 1. F is1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine, thecompound of instant Example 2. H isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN ®123, CIBA.

These data show that an instant compound (Compound E or F) incombination with a benzotriazole UV absorber protects the gray scentedcandle wax from unwanted discoloration far better than conventionalstabilizer systems.

EXAMPLE 6 Color Fade of White Scented Candle Wax under Fluorescent LampExposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 24 days Blank (no add) 34.34 D (0.3%) 32.33A (0.3%) 29.16 B (0.15%) + 20.08 C (0.15%) A (0.15%) + 31.06 D (0.15%) A(0.15%) + 15.33 F (0.15%) G (0.15%) + 12.82 E (0.15%) G (0.15%) + 16.82F (0.15%) G (0.15%) + 12.96 F (0.3%) A (0.15%) + 10.99 E (0.15%) A(0.15%) + 7.29 E (0.3%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMMASORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine,the compound of instant Example 1. F is1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine, thecompound of instant Example 2. G is2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine,TINUVIN ® 400, CIBA.

These data show that an instant compound (Compound E or F) incombination with a UV absorber, particularly a benzotriazole UVabsorber, protects the white scented candle wax from unwanteddiscoloration far better than conventional stabilizer systems.

EXAMPLE 7 Color Fade of White Scented Candle Wax under UV Lamp Exposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 25 days Blank (no add) 45.09 D (0.3%) 32.03A (0.3%) 25.50 B (0.15%) + 30.11 C (0.15%) A (0.15%) + 29.74 D (0.15%) G(0.15%) + 24.89 E (0.15%) A (0.15%) + 20.14 F (0.15%) A (0.15%) + 17.13E (0.15%) A (0.15%) + 14.66 E (0.3%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMMASORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is2,4-bis[N-n-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[2-(C₂₀-C₄₀alkanoyloxy)ethyl]amino-s-triazine,the compound of instant Example 1. F is1-cyclohexyloxy-2,2,6,6-tetramethyl-4-C₂₀-C₄₀alkanoyloxypiperidine, thecompound of instant Example 2. G is2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine,TINUVIN ® 400, CIBA.

These data show that an instant compound (Compound E or F) incombination with a UV absorber, particularly a benzotriazole UVabsorber, protects the white scented candle wax from unwanteddiscoloration far better than conventional stabilizer systems.

EXAMPLE 8 Thermal Permanence of the Instant Compounds

The instant compounds are subjected to thermogravimetric analysis tomeasure their thermal permanence relative to the commercial hinderedamine stabilizer, TINUVIN® 770.

Temperature ° C. Temperature ° C. Compound at 10% wt loss at 50% wt lossTINUVIN ® 255 297 770* Example 1 284 368 *TINUVIN ® 770 isbis(2,2,6,6-tetramethylpiperidin-4yl) sebacate, CIBA.

These data show the improved thermal permanence of the instant compoundscompared to the commerical hindered amine stabilizer TINUVIN® 770.

EXAMPLE 9 Preparation of LDPE Films for HALS Migration Values

Ground low density polyethylene powder (Dow 640 I) is tumble blendedwith the desired quantity of test long chain hindered amine (HALS) and0.30% by weight of Superfloss antiblock agent. The blended resin istwin-screw compounded at 450° F. (232° C.). The resulting pellets areblown at 400° F. (204° C.) into a monolayer film of approximately 3 milthickness.

Blown films are used to study the migration of the test HALS from theinterior of the film to the film surface. Additives that migrate tend toproduce a white deposit on the film surface which can be easily scrapedoff. This is the phenomenon called blooming. It is clear that, if theadditive blooms on to the surface of the film and is easily removedtherefrom, it cannot serve to protect the film itself which is itspurpose.

Visual assessment of the film surface is performed at approximately 30day intervals up to 375 days. The films are stored at room temperature.

The instant long chain hindered amine compounds are particularlyeffective in LDPE films in the prevention of blooming because of theirnon-migration properties.

EXAMPLE 10 PET Bottles

Poly(ethylene terephthalate), PET, concentrates (10% by weight) of theinstant long chain hindered amine compounds are prepared using Eastapak9921W PET, on a 27 mm twin screw extruder at an operating temperature atthe die of 275° C. The concentrates are let down with base resin to thefinal additives loading of 0.3% by weight based on resin. PET is driedunder vacuum for at least four hours at 240° F. prior to preformmolding. Preforms are molded on a unit cavity Arburg press using theminimum injection temperature and back pressure necessary to obtainparts free of haze and crystallinity. Bottle blow molding is conductedusing a Sidel SBO ⅔ blow molding machine, using preforms describedabove. Bottle wall thickness of 0.015-0.016 inches is achieved.

The instant compounds are particular eficacious because of their abilityto protect the resin from unwanted degradation and without migrationinto the bottle contents.

EXAMPLE 11

To separate poly(ethylene terephthalate), PET, resin formulationscontaining 0.5% by weight of the instant long chain hindered amine areadded 0.5% by weight of each of the following benzotriazole stabilizers:

(a)5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(b) isooctyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(c) 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(d)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(e)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(f)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

(g) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

(h)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(i)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(j)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(k)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(l)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;or

(m) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate.

Each of the stabilized resin compositions are then blow or injectionmolded into a PET bottle having incorporated therein each of therespective UV absorbers. The PET bottles are especially effective atprotecting the contents therein from UV radiation allowing for a longershelf like for the product contained in the bottle.

EXAMPLE 12

To separate poly(ethylene terephthalate), PET, resin formulationscontaining 0.5% by weight of the instant long chain hindered amine areadded 0.5% by weight of each of the following benzotriazole stabilizers:

(i)2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethyideneoxyphenyl)-s-triazine;

(ii)2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

(iii)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;

(iv)2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine;

(v)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine;(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups)

(vi)methylenebis-[2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine,methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio;

(vii)2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;

(viii)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine;

(ix)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxy-phenyl)-s-triazine;CYASORB® 1164, Cytec;

(x)2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;or

(xi)2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine.

Each of the stabilized resin compositions are then blow or injectionmolded into a PET bottle having incorporated therein each of therespective UV absorbers. The PET bottles are especially effective atprotecting the contents therein from UV radiation allowing for a longershelf like for the product contained in the bottle.

EXAMPLE 13

A multi-layer bottle is prepared wherein the exterior layer and theinnermost layer contacting the bottle contents are composed of PET andwhich also comprises a barrier layer. When one or more of thebenzotriazoles or s-triazine UV absorbers listed in Examples 11 and 12and an instant long chain hindered amine are incorporated into any ofthe three layers at 0.5% by weight based on the weight of the resin, thecontents of the bottle are effectively protected from UV radiation.

EXAMPLE 14

A multi-layer bottle is prepared wherein the exterior layer and theinnermost layer contacting the bottle contents are composed of HDPE(high density polyethylene) and which also comprises a barrier layer.When one or more of the benzotriazoles or s-triazine UV absorbers listedin Examples 11 and 12 and an instant long chain hindered amine areincorporated into any of the three layers at 0.5% by weight based on theweight of the resin, the contents of the bottle are effectivelyprotected from UV radiation.

EXAMPLE 15

A multi-layer bottle is prepared wherein the exterior layer and theinnermost layer contacting the bottle contents are composed ofpolypropylene and which also comprises a barrier layer. When one or moreof the benzotriazoles or s-triazine UV absorbers listed in Examples 11and 12 and an instant long chain hindered amine are incorporated intoany of the three layers at 0.5% by weight based on the weight of theresin, the contents of the bottle are effectively protected from UVradiation. The compounds listed under Examples 16 to 46 are preparedfollowing the general procedures found in Examples 1 and 2 and in theU.S. Pat. Nos. 5,204,473; 5,216,156; 5,844,026 and 6,166,212.

EXAMPLES 16-24

(1)

Ex* E₅ E₉ E** R₂** T₁ 16 OE₉ methyl — —COT₁ C₄₀-C₆₀ — 17 OE₉ octyl ——COT₁ C₂₀-C₄₀ — 18 OE₉ benzyl — —COT₁ C₈₀-C₁₀₀ — 19 OE₉ cyclo- — AC₂₀-C₄₀ m is 4; hexenyl X is —O— 20* OE₉ octadecyl — B C₈₀-C₁₀₀ p is 10;X is NCH₃ 21 OE(OH)_(b) — C —COT₁ C₂₀-C₄₀ b is 1 22* OE(OH)_(b) — D—COT₁ C₆₀-C₈₀ b is 2 23 OE(OH)_(b) — C —COXT₁ C₂₀-C₄₀ b is 1 24OE(OH)_(b) — C —COT₁ C₄₀-C₆₀ b is 1 *Unless otherwise noted, G₁ to G₄are each methyl. In Example 20, G₁ and G₃ are each methyl, and G₂ and G₄are each ethyl. In Example 22, G₁ to G₄ are n-propyl. **A is—(CH₂)_(m)CO—X—T₁. B is —(CH₂)_(p)—X—CO—T₁. C is —CH₂C(CH₃)₂—OH. D is—CH₂CH(OH)—CH₂OH.

EXAMPLES 25-32

(2)

Ex* E₅ E₉ E** R₂** T₁ 25 OE₉ methyl — —COT₁ C₂₀-C₄₀ R₄ is CH₃ 26 OE₉cyclo- — —COT₁ C₄₀-C₆₀ R₄ is H hexyl 27 OE₉ octyl — —COT₁ C₈₀-C₁₀₀ R₄ =C₄H₉ 28 OE₉ phenyl — E C₂₀-C₄₀ m is 6; X is —O—; R₄ is H 29* OE(OH)_(b)— C —COT₁ C₂₀-C₄₀ R₄ is CH₃; b is 1 30* OE(OH)_(b) — D T₁ C₄₀-C₆₀ b is2; R₄ is H 31 OE(OH)_(b) — C A C₂₀-C₄₀ b is 1; R₄ is H; p is 3 32OE(OH)_(b) — C F C₂₀-C₄₀ b is 1; R₄ is CH₃; p is 6 *Unless otherwisenoted, G₁ to G₄ are each methyl. In Example 30, G₁ and G₃ are eachoctyl, and G₂ and G₄ are each methyl. **A is —(CH₂)_(m)CO—X—T₁. C is—CH₂C(CH₃)₂—OH. D is —CH₂CH(OH)—CH₂OH. E is —(CH₂)_(m)CO—T₁. F is—CO—(CH₂)_(p)—X—CO—T₁.

EXAMPLES 33-40

(3)

Ex* E₅ E₉ E** R₆** T₁ 33 OE₉ methyl — —XT₁ C₂₀-C₄₀ X is —O— 34 OE₉cyclo- — —XT₁ C₄₀-C₆₀ X is —O— hexyl 35 OE₉ octyl — —XT₁ C₂₀-C₄₀ X is—NH— 36 OE₉ phenyl — G C₂₀-C₄₀ m is 6; X is —O—; X₁ is —O— 37 OE₉ allyl— —XT₁ C₂₀-C₄₀ X is —O— 38 OE(OH)_(b) — C —XT₁ C₂₀-C₄₀ b is 1 39OE(OH)_(b) — C —XT₁ C₂₀-C₄₀ b is 1; X is NCH₃ 40 OE(OH)_(b) — H IC₂₀-C₄₀ b is 2; p is 3; X is NCH₃; X₁ is —O— *Unless otherwise noted, G₁to G₄ are each methyl. **C is —CH₂C(CH₃)₂—OH. G is—X—(CH₂)_(m)—CO—X₁—T₁. H is —CH₂—CH(OH)—CH₂CH₂OH. I is—X—(CH₂)_(p)—X₁—CO—T₁.

EXAMPLES 41-46

(4)

Ex* E₅ E₉ E** R₇** T₁ 41 OE₉ methyl — I C₂₀-C₄₀ X is —O—; X₁ is —NH—; pis 2; R₈ is NHT₂; R₉ is NC₄H₉ 42 OE₉ octyl — —XT₁ C₂₀-C₄₀ X is —O—; R₈is —OT₂; R₉ is —O— 43 OE₉ allyl — —XT₁ C₄₀-C₆₀ X is —O—; R₈ is —XT₁ 44OE₉ cyclo- — G C₂₀-C₄₀ m is 3; X is —O—; X₁ is NCH₃; R₈ = NC₄H₉T₂; R₉ =NC₄H₉ 45 OE(OH)_(b) — C I C₂₀-C₄₀ X₁ is —O—; b is 1; p is 2; X is —NH—′R₈ = NC₄H₉T₂; R₉ = NC₄H₉ 46 OE(OH)_(b) — C —XT₁ C₄₀-C₆₀ b is 1 R₈ is—OT₂; R₉ is —O—; X is —O— *Unless otherwise noted, G₁ to G₄ are eachmethyl. **C is —CH₂C(CH₃)₂—OH. G is —X—(CH₂)_(m)—CO—X₁—T₁. I is—X—(CH₂)_(p)—X₁—CO—T₁.

What is claimed is:
 1. A composition which comprises (a) candle wax which is white and unscented; white and scented; dyed and unscented; dyed and scented; dipped and unscented; or dipped and scented, and (b) an effective stabilizing amount of a combination of (i) a long chain hindered amine piperidine compound of formula 4, 5 or 6 and (ii) a UV absorber or an antioxidant, or a UV absorber and an antioxidant wherein the ratio by weight of (i) to (ii) is from 10:1 to 1:10, and where the compound of formula 4, 5 or 6 is

where G₁, G₂, G₃, and G₄ are independently alkyl of 1 to 8 carbon atoms, or G₁ and G₂ together are pentamethylene, or G₃ and G₄ together are pentamethylene; E₅ is OE₉ or —O—E—(OH)_(b); E₉ is straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, straight or branched chain alkenyl of 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms; or a group of formula IV

E₁₁ to E₁₅ are independently hydrogen, halogen, nitro, cyano, alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy or 1 to 18 carbon atoms, phenylalkoxy of 7 to 15 carbon atoms, aryloxy of 6 to 10 carbon atoms, alkylcarbonyloxy of 2 to 18 carbon atoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15 carbon atoms, sulfo or phosphono, or any two vicinal substituents connected together to form a mono- or polycyclic ring; E is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in E, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atom of E; R₇ and R₈ are independently chlorine, alkoxy of 1 to 18 carbon atoms, —O—T₂, amino substituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18 carbon atoms, —N(alkyl)T2 with alkyl of 1 to 18 carbon atoms, —N(alkyl)2 of 2 to 36 carbon atoms, —X—T₁, X-(CH₂)_(m)—CO—X₁T₁, or X-(CH₂)_(p)—X₁—CO—T₁; T₁ is straight or branched chain alkyl of 19 to 100 carbon atoms, or said alkyl substituted by one hydroxyl group and interrupted by one oxa moiety, or a mixture of such alkyl moieties; or T₁ is —(R—O)_(n)—R—OG₅ where R is ethylene, propylene, trimethylene, 1,2-butylene or tetramethylene, and n is 4 to 49 so that the total number of carbon atoms in T₁ is at least 20; G₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; X and X₁ are independently —O—, or —N—(R₄)—; R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms; m is 1 to 12; p is 1 to 12; R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atom substituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₂

E₆ is hydrogen, oxyl, hydroxyl, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 3 to 24 carbon atoms, benzyl, acetyl, —CH₂CH(OH)—E₈, —OE₉, or, —OE(OH)_(b); E₈ is hydrogen, methyl, ethyl or phenyl; R₁₀ is hydrogen or an alkyl group of 1 to 18 carbon atoms; q is 2 to 8; y is 1 to 10; R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 18 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T₂ with alkyl of 1 to 8 carbon atoms, —N(alkyl)₂ of 2 to 16 carbon atoms, —X—T₁, X-(CH₂)_(m)—CO—X₁—Ti, or X-(CH₂)_(p)-X₁—CO—T₁; R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R₁₅, or s-triazinyl substituted twice by R₁₅ with the condition that the two R₁₅ substituents may be different; R₁₇ is chlorine, amino substituted by alkyl of 1 to 18 carbon atoms or by T₂, —N(alkyl)T₂ with alkyl of 1 to 8 carbon atoms, —N(alkyl)₂ of 2 to 16 carbon atoms, or the group T₃

R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by —N(alkyl)2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms; with the proviso that at least one of R₇, R₈, or R₁₅ is a group which contains a T₁ moiety.
 2. A composition according to claim 1 where the ratio by weight of (i) to (ii) is from 4:1 to 1:4.
 3. A composition according to claim 2 where the ratio by weight of (i) to (ii) is from 2:1 to 1:2.
 4. A composition according to claim 1 where the effective amount of the UV absorber plus the long chain hindered amine compound in the candle wax is 0.01 to 10% by weight based on the wax.
 5. A composition according to claim 4 where the effective amount of the UV absorber plus long chain hindered amine compound in the candle wax is 0.1 to 2% by weight based on the wax.
 6. A composition according to claim 5 where the effective amount of the UV absorber plus long chain hindered amine compound in the candle wax is 0.1 to 0.5% by weight based on the wax.
 7. A composition according to claim 1 wherein the UV absorber of component (ii) is a benzotriazole, a benzophenone, an α-cyanoacrylate, an oxanilide, an s-triazine, a cinnamate, a malonate, a benzoate or a salicylate, or a mixture thereof.
 8. A composition according to claim 7 wherein the UV absorber is a benzotriazole, a benzophenone or an s-triazine.
 9. A composition according to claim 7 wherein the UV absorber is (a) 4-octyloxy-2-hydroxybenzophenone; (b) 4-methoxy-2-hydroxybenzophenone; (c) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; (d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole; (e) 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; (f) octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; (g) 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; (h) 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole; (i) 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; (j) 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; (k) 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole; (l) 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole; (m) 2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole; (n) 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole; (o) 2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole; (p) 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole; (q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole, (r) 2-ethylhexyl p-methoxycinnamate; (s) 4-methoxy-2,2′-dihydroxybenzophenone; (t) 4,4′dimethoxy-2,2′-dihydroxybenzophenone; (u) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; (v) 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; (w) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine; (x) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5-α-cumylphenyl]-s-triazine; (y) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine with octyl α-haloacetate; or (z) the mixture of 3,3;3,5;5,5-methylene-bis[2,4-bis(2,4-dimethylphenyl)]-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxyphenyl)]-s-triazine.
 10. A composition according to claim 9 wherein the UV absorber is (a) 4-octyloxy-2-hydroxybenzophenone; (b) 4-methoxy-2-hydroxybenzophenone; (d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole; (o) 2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole; (p) 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole; (q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole; (y) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine with octyl α-haloacetate; or (z) the mixture of 3,3;3,5;5,5-methylene-bis[2,4-bis(2,4-dimethylphenyl)]-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxyphenyl)]-s-triazine.
 11. A composition according to claim 1 wherein the antioxidant is a phenolic antioxidant, phosphite, nitrone, amine oxide or hydroxylamine, or mixture thereof.
 12. A composition according to claim 1 wherein the effective amount of UV absorber in combination with the long chain hindered amine compound and an antioxidant is 0.01 to 10% by weight based on the wax.
 13. A composition according to claim 12 wherein the effective amount of UV absorber in combination with the long chain hindered amine compound and an antioxidant is 0.1 to 2% by weight based on the wax.
 14. A composition according to claim 13 wherein the effective amount of UV absorber in combination with the long chain hindered amine compound and an antioxidant is 0.1 to 0.5% by weight based on the wax.
 15. A composition according to claim 1 wherein the antioxidant is n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, N,N-di-(C₁₂-C₂₄alkyl)-N-methyl-amine oxide, or N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine by direct oxidation.
 16. A composition according to claim 15 wherein the antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol, or 2,2′-ethylidene-bis(4,6-di-tert-butylphenol). 